EP2791388B1 - Electroless plating of silver onto graphite - Google Patents
Electroless plating of silver onto graphite Download PDFInfo
- Publication number
- EP2791388B1 EP2791388B1 EP12856639.5A EP12856639A EP2791388B1 EP 2791388 B1 EP2791388 B1 EP 2791388B1 EP 12856639 A EP12856639 A EP 12856639A EP 2791388 B1 EP2791388 B1 EP 2791388B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- silver
- graphite
- composition
- plating
- silver salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 99
- 229910002804 graphite Inorganic materials 0.000 title claims description 88
- 239000010439 graphite Substances 0.000 title claims description 88
- 229910052709 silver Inorganic materials 0.000 title claims description 52
- 239000004332 silver Substances 0.000 title claims description 49
- 238000007772 electroless plating Methods 0.000 title claims description 10
- 239000000203 mixture Substances 0.000 claims description 112
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 49
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 48
- 238000007747 plating Methods 0.000 claims description 44
- 230000004913 activation Effects 0.000 claims description 32
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 30
- 229910000077 silane Inorganic materials 0.000 claims description 27
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 17
- 239000003638 chemical reducing agent Substances 0.000 claims description 15
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 14
- 238000005580 one pot reaction Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 239000000908 ammonium hydroxide Substances 0.000 claims description 9
- 239000008139 complexing agent Substances 0.000 claims description 9
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 8
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 6
- JTXUAHIMULPXKY-UHFFFAOYSA-N 3-trihydroxysilylpropan-1-amine Chemical compound NCCC[Si](O)(O)O JTXUAHIMULPXKY-UHFFFAOYSA-N 0.000 claims description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- VGIURMCNTDVGJM-UHFFFAOYSA-N 4-triethoxysilylbutanenitrile Chemical compound CCO[Si](OCC)(OCC)CCCC#N VGIURMCNTDVGJM-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- WBUSESIMOZDSHU-UHFFFAOYSA-N 3-(4,5-dihydroimidazol-1-yl)propyl-triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN1CCN=C1 WBUSESIMOZDSHU-UHFFFAOYSA-N 0.000 claims description 3
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 3
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 3
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 claims description 3
- GBQYMXVQHATSCC-UHFFFAOYSA-N 3-triethoxysilylpropanenitrile Chemical compound CCO[Si](OCC)(OCC)CCC#N GBQYMXVQHATSCC-UHFFFAOYSA-N 0.000 claims description 3
- HKMVWLQFAYGKSI-UHFFFAOYSA-N 3-triethoxysilylpropyl thiocyanate Chemical compound CCO[Si](OCC)(OCC)CCCSC#N HKMVWLQFAYGKSI-UHFFFAOYSA-N 0.000 claims description 3
- KVUMYOWDFZAGPN-UHFFFAOYSA-N 3-trimethoxysilylpropanenitrile Chemical compound CO[Si](OC)(OC)CCC#N KVUMYOWDFZAGPN-UHFFFAOYSA-N 0.000 claims description 3
- YSEVGVGBHWFTIF-UHFFFAOYSA-N 4-[dimethoxy(methyl)silyl]butanenitrile Chemical compound CO[Si](C)(OC)CCCC#N YSEVGVGBHWFTIF-UHFFFAOYSA-N 0.000 claims description 3
- SWDDLRSGGCWDPH-UHFFFAOYSA-N 4-triethoxysilylbutan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCCN SWDDLRSGGCWDPH-UHFFFAOYSA-N 0.000 claims description 3
- CNODSORTHKVDEM-UHFFFAOYSA-N 4-trimethoxysilylaniline Chemical compound CO[Si](OC)(OC)C1=CC=C(N)C=C1 CNODSORTHKVDEM-UHFFFAOYSA-N 0.000 claims description 3
- FPJPAIQDDFIEKJ-UHFFFAOYSA-N 4-trimethoxysilylbutanenitrile Chemical compound CO[Si](OC)(OC)CCCC#N FPJPAIQDDFIEKJ-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 150000002016 disaccharides Chemical class 0.000 claims description 3
- 150000004676 glycans Chemical class 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 150000002772 monosaccharides Chemical class 0.000 claims description 3
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 3
- QNHNSPNFZFBEQR-UHFFFAOYSA-N n'-(3-trihydroxysilylpropyl)ethane-1,2-diamine Chemical compound NCCNCCC[Si](O)(O)O QNHNSPNFZFBEQR-UHFFFAOYSA-N 0.000 claims description 3
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- 229920001282 polysaccharide Polymers 0.000 claims description 3
- 239000005017 polysaccharide Substances 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 150000003892 tartrate salts Chemical class 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 21
- 238000009472 formulation Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 239000012190 activator Substances 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000004593 Epoxy Substances 0.000 description 10
- 239000000523 sample Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000007770 graphite material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 4
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000008313 sensitization Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 2
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 229940015043 glyoxal Drugs 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 nitrogen-containing silanes Chemical class 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- JNKQKOKSOYJQIZ-UHFFFAOYSA-O azanium;silver;dinitrate Chemical compound [NH4+].[Ag+].[O-][N+]([O-])=O.[O-][N+]([O-])=O JNKQKOKSOYJQIZ-UHFFFAOYSA-O 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000012864 cross contamination Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1658—Process features with two steps starting with metal deposition followed by addition of reducing agent
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
- C23C18/1882—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1889—Multistep pretreatment with use of metal first
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
Definitions
- This invention is related to the electroless plating of silver onto graphite powder.
- Silver-plated copper is one of the best alternatives due to its excellent initial conductivity. However, copper lacks oxidative stability, which limits its use in applications requiring high reliability at high temperature and high humidity conditions. Moreover, silver-plated copper itself is relatively expensive. Silver-plated glass or any other silver-plated filler with an insulator core suffer low conductive performance, and are poor substitutes for silver or silver-plated copper.
- Silver-coated graphite is lower in cost than, and can deliver comparable initial conductivity to, bulk silver or silver-plated copper, without the oxidative stability problems associated with copper.
- Current processes for preparing silver-coated graphite suffer from production difficulties.
- graphite pretreatment methods involve at least one of the following steps: oxidation, heating, or wet chemical activation, followed by powder separation, washing and rinsing. All these procedures lead to problems for large-scale manufacture.
- Oxidation is effective to introduce active sites on graphite surfaces for plating, but typical oxidants, such as nitric acid, sulfuric acid, or hydrogen peroxide, require special operation procedures due to their corrosive or explosive nature. In addition, powder separation, washing and rinsing generate hazardous waste.
- Heating is another method to generate active surfaces on graphite.
- heating requires special equipment, there is a narrow temperature window for operation, and it is difficult to reproduce results.
- Typical wet activation methods involve the use of tin or similar metal compounds, along with a sensitizer, such as, palladium chloride in aqueous condition. After sufficient mixing, the graphite powder must be separated from the activation bath using numerous filtration, washing and rinsing steps, taking time and creating hazardous waste.
- CN 101 054 483 A discloses one of such methods.
- the current invention circumvents these problems.
- This invention is a one-pot process for the electroless-plating of silver onto graphite powder. No powder pretreatment steps for the graphite, which typically require filtration, washing or rinsing, are required.
- the inventive process comprises mixing together three reactant compositions in water. These can be added together simultaneously or in a combination of stages.
- the first composition is an aqueous graphite activation composition comprising graphite powder and a functional silane.
- the functional silane interacts both with the graphite in this activation composition and with a silver salt that is a component of the silver-plating composition.
- the second composition a silver-plating composition, comprises a silver salt (which interacts with the functional silane) and a silver complexing agent. These can be provided as solids or in an aqueous solution.
- the third composition a reducing composition, comprises a reducing agent for the silver salt, which can be provided as a solid or in an aqueous solution.
- the aqueous graphite activation composition comprises graphite powder and a nitrogen-containing silane.
- the silane is either a siloxane or a silanol.
- Graphite powder has a minor amount (in the ppm range) of oxygen associated on its surface; the oxygen is capable of interacting in aqueous conditions with the silane in the nitrogen-containing silane to form silanol groups by hydrolysis. This reaction anchors the nitrogen-containing silane to the graphite.
- the nitrogen in the nitrogen-containing silane in turn will coordinate with the silver salt in the silver-plating composition. This coordination provides an activation or seeding site for plating silver on the whole graphite surface.
- Exemplary nitrogen-containing silanes include 3-isocyanatopropyltri-ethoxysilane, 3-isocyanatopropyltrimethoxysilane, 2-cyanoethyltrimethoxy-silane; 2-cyanoethyltriethoxysilane, 3-cyanopropyltri-methoxysilane, 3-cyano-propyltriethoxysilane, 3-cyanopropylmethyldimethoxysilane, 3-aminopropyl-trimethoxy-silane, 3-aminopropyltriethoxysilane, 3-amino-propylmethyl-dimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-amino-butyltriethoxy-silane, N-(2-amino-ethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrieth
- the nitrogen-containing silane is present in the graphite activation composition in an amount of 0.01-20 weight% of graphite weight, preferably at 0.1-10 wt% of graphite weight.
- the silver-plating composition comprises a silver salt and a silver complexing agent.
- the silver salt is water soluble.
- Exemplary silver salts include silver nitrate, silver sulfate, and silver chloride.
- the silver salt is silver nitrate.
- the concentration of silver salt in the plating bath ranges from 0.01 to 50 g/L. In one embodiment, the silver salt concentration ranges from 2 to 30 g/L. In a further embodiment, the silver salt concentration ranges from 5 to 25 g/L.
- Exemplary silver complexing agents include ammonium hydroxide, ethylenediamine, methylamine, and ethylamine.
- the complexing agent is ammonium hydroxide in an aqueous solution within the range of 28 to 30 wt% (weight percent).
- the amount of 28 to 30 wt% ammonium hydroxide solution present in the plating bath ranges from 0.01 to 35 g/L; in one embodiment, from 1.4 to 20 g/L; in a further embodiment, from 3.5 to 18 g/L.
- the silver-plating composition can be mixed in conjunction with the graphite activation composition or added separately, after the graphite composition is formed and mixed.
- the reducing composition comprises a reducing agent for the silver salt.
- exemplary reducing agents include aldehydes, polyols, tartrates, tartaric acid, monosaccharides, disaccharides, polysaccharides, hydrazine, hydrazine hydrate, and phenyl hydrazine.
- the reducing agent is formaldehyde (typically as a 37 wt% aqueous solution) and/or glyoxal (typically as a 40 wt% aqueous solution).
- the amount of 37wt% aqueous formaldehyde solution present in the plating composition ranges from about 0.01 to 150g/L; in another embodiment, from 1 to 100 g/L; in a further embodiment, from 5 to 50 g/L.
- the reducing composition is added to the combination of the graphite activation composition and the silver-plating composition.
- pH-control substance is optional.
- pH control agents include KOH, NaOH, or any ammonium, nitrate, or borate salt.
- organic co-solvent examples include alcohol, acetone, tetrahydrofuran (THF), ethyl acetate, and toluene.
- the process of this invention comprises (A) mixing together in water the following compositions: (1) a graphite activation composition comprising graphite powder and a nitrogen-containing silane; (2) a silver-plating composition comprising a silver salt and a silver complexing agent; and (3) a reducing composition for the silver salt; and (B) isolating the resultant silver-coated graphite.
- the components within each of the graphite activation and silver-plating compositions can be mixed together all at once, or they can be mixed in stages with a time delay between additions of the components for mixing to occur. (The reducing composition has only one component.) Mixing is typically accomplished by stirring at room temperature.
- a portion of the silver salt that would make up the silver-plating composition is added to the graphite activation composition.
- This portion of the silver salt will be an amount within the range of 0.1 wt% to 10 wt% of the total graphite weight.
- the silver salt is added to the graphite activation composition in an amount within the range of 1 wt% to 5 wt% of the total graphite weight.
- the silver-plating composition, less the amount of silver salt previously added to the graphite activation composition, is then added to the graphite activation composition and mixed. To this mixture is added the reducing composition for the silver salt.
- the mixture of compositions is stirred together at a temperature sufficient to cause the silver salt to be reduced and plated onto the graphite.
- the preferred mixing temperature or range of mixing temperatures is within the range of 20°C to 25°C.
- the typical reaction time is under one hour for laboratory quantities; however, longer times can be expected for commercial quantities.
- Glyoxal is a possible substitute for formaldehyde; however, it is less reactive and requires a higher reaction temperature and longer mixing. A benefit is that it has less toxicity.
- the graphite activation, silver-plating, and reducing compositions can be mixed together without any time delay between addition of the compositions to each other.
- the addition takes place sequentially so that the graphite activation composition is prepared first and mixed for a time; then the silver-plating composition (prepared and mixed) is added to the graphite activation composition.
- the graphite activation and silver-plating compositions are mixed for a time, after which the reducing composition (prepared and mixed) is added to the combination of the graphite activation and silver-plating compositions, and all three compositions are mixed. Mixing is typically accomplished by stirring at room temperature.
- Example 1 The graphite activation composition and the silver-plating composition were prepared as one composition together, after which the reducing composition was added. The compositions were prepared and mixed at room temperature.
- Example 2 The graphite activation composition, containing a small amount of silver nitrate as a seeding compound, was prepared independently of the silver-plating composition. The compositions were prepared and mixed at room temperature.
- Example 3 A seed solution of silver nitrate was added to a prepared and stirred graphite activation composition. Subsequently, the silver-plating composition was added. The compositions were prepared and mixed at room temperature.
- Example 4 Comparative.
- a prior art multi-step electroless plating method is described as a conventional way of preparing silver-coated graphite material.
- the method includes the use of graphite activation, graphite sensitization, and plating baths. Moving from bath to bath requires separation of solution and powder product in order to minimize cross contamination of the baths.
- the sensitized graphite mixture was then washed with 200g water followed by centrifugation until the solution pH reached between 5-6.
- An aqueous silver plating solution containing silver nitrate (11 g), ammonium hydroxide (28 wt%, 9 g) and water (1100mL) was added with stirring to the sensitized graphite mixture.
- a mixture of reducing agent containing formaldehyde (37 wt%) aqueous solution (10 g).
- Silver-coated graphite product formed within 15 minutes and settled to the bottom of the reaction flask.
- the clear aqueous layer was decanted off and the silver-coated graphite product washed three times with 200g of water each time, followed by drying at 120°C overnight. The yield was above 95%.
- Conductive adhesive formulations were prepared from each of the silver-coated graphite products from examples 1 to 4 using an epoxy resin (EPICLON 835 LV from DIC formally known as Dainippon Ink and Chemical) at a 32 volume% (vol%) loading of the silver-coated graphite, and one weight% (wt%) of 2-ethyl-4-methyl imidazole based on total weight.
- EPICLON 835 LV from DIC formally known as Dainippon Ink and Chemical
- Films of the formulations were cast on glass slides and cured at 175°C for one hour in an air oven.
- volume resistivity was tested using a four-probe testing method at room temperature.
- the resistivities were the following: Example 1 2 3 4 Method One-pot One-pot One-pot Multiple baths VR in 32 vol% (epoxy) (ohm ⁇ cm) 1.36E-03 1.34E-03 1.52E-03 3.21E-03
- Example 6 Conductivity Performance in Acrylate Formulations. Conductive adhesive formulations were prepared from each of the silver-coated graphite products from examples 1 to 4 using an acrylate formulation at a 26 vol% loading of the silver-coated graphite (or about 60wt% filler loading based on total weight).
- the acrylate composition contained 49 wt% tricyclodecane dimethanol diacrylate, 46 wt% isobornyl methacrylate, and 5 wt% dicumin peroxide.
- Films of the formulations were cast on glass slides and cured at 175°C for one hour in an N 2 oven.
- volume resistivity was tested using a four-probe testing method at room temperature.
- the resistivities were the following: Example 1 2 3 4 Method One-pot One-pot One-pot Multiple baths VR in 26vol% (acrylate) (ohm ⁇ cm) 4.2 E-03 1.6 E-03 1.5 E-03 1.4 E-02
- SCG Silver-coated graphite samples
- Adhesive formulations were prepared using the silver-coated graphite (SCG) and its comparative sample.
- Adhesive resin was either an epoxy composition or an acrylate composition.
- the epoxy compositions contained epoxy resin (EPICLON 835 LV from DIC formally known as Dainippon Ink and Chemical) with 2.5 wt% 2-ethyl-4-methyl-imidazole.
- the acrylate compositions contained 49% tricyclodecane dimethanol diacrylate, 46 wt % isobornyl methacrylate, and 5 wt % dicumin peroxide.
- the silane activator was 3-isocyanatopropyltri-ethoxylsilane (ICPTES).
- Films of the formulations were cast on glass slides.
- the epoxy formulations were cured at 175°C for one hour in an air oven.
- the acrylate formulations were cured at 175°C for one hour in an N 2 oven.
- volume resistivity was measured using a four-probe testing method at room temperature.
- Example 8 Varying Nitrogen-Containing Silane Activators.
- SCG samples were prepared according to example 2 with a nitrogen-containing silane activator as listed in the following table.
- Conductive adhesive formulations were prepared from each of the silver-coated graphite samples using an epoxy resin (EPICLON 835 LV from DIC formally known as Dainippon Ink and Chemical) at a 26 vol% loading of the silver-coated graphite, and one wt% of 2-ethyl-4-methyl imidazole based on total weight.
- EPICLON 835 LV from DIC formally known as Dainippon Ink and Chemical
- Films of the formulations were cast on glass slides.
- the epoxy formulations were cured at 175°C for one hour in an air oven.
- volume resistivity was measured using a four-probe testing method at room temperature.
- SCG samples were prepared according to example 2, and were formulated with different concentrations of silane activator, silver nitrate seed, silver nitrate in plating solution, and reducing agent.
- Conductive adhesive formulations were prepared from each of the silver-coated graphite samples and an epoxy resin (EPICLON 835 LV from DIC formally known as Dainippon Ink and Chemical) at a 26 vol% loading of the silver-coated graphite, and one wt% of 2-ethyl-4-methyl imidazole based on total weight.
- EPICLON 835 LV from DIC formally known as Dainippon Ink and Chemical
- the epoxy formulations were cured at 175°C for one hour in an air oven.
- volume resistivity was measured using a four-probe testing method at room temperature.
Description
- This invention is related to the electroless plating of silver onto graphite powder.
- Bulk silver continues to increase in cost, prompting the search for alternatives for use in the fabrication, for example, of semiconductors and electronic devices. Silver-plated copper is one of the best alternatives due to its excellent initial conductivity. However, copper lacks oxidative stability, which limits its use in applications requiring high reliability at high temperature and high humidity conditions. Moreover, silver-plated copper itself is relatively expensive. Silver-plated glass or any other silver-plated filler with an insulator core suffer low conductive performance, and are poor substitutes for silver or silver-plated copper.
- Silver-coated graphite is lower in cost than, and can deliver comparable initial conductivity to, bulk silver or silver-plated copper, without the oxidative stability problems associated with copper. Current processes for preparing silver-coated graphite, however, suffer from production difficulties.
- The surface of graphite is inert and must be pretreated before it can be plated in an electroless process. However, graphite pretreatment methods involve at least one of the following steps: oxidation, heating, or wet chemical activation, followed by powder separation, washing and rinsing. All these procedures lead to problems for large-scale manufacture.
- Oxidation is effective to introduce active sites on graphite surfaces for plating, but typical oxidants, such as nitric acid, sulfuric acid, or hydrogen peroxide, require special operation procedures due to their corrosive or explosive nature. In addition, powder separation, washing and rinsing generate hazardous waste.
- Heating is another method to generate active surfaces on graphite. However, heating requires special equipment, there is a narrow temperature window for operation, and it is difficult to reproduce results.
- Typical wet activation methods involve the use of tin or similar metal compounds, along with a sensitizer, such as, palladium chloride in aqueous condition. After sufficient mixing, the graphite powder must be separated from the activation bath using numerous filtration, washing and rinsing steps, taking time and creating hazardous waste.
CN 101 054 483 A discloses one of such methods. - The current invention circumvents these problems.
- This invention is a one-pot process for the electroless-plating of silver onto graphite powder. No powder pretreatment steps for the graphite, which typically require filtration, washing or rinsing, are required.
- The inventive process comprises mixing together three reactant compositions in water. These can be added together simultaneously or in a combination of stages.
- The first composition is an aqueous graphite activation composition comprising graphite powder and a functional silane. The functional silane interacts both with the graphite in this activation composition and with a silver salt that is a component of the silver-plating composition.
- The second composition, a silver-plating composition, comprises a silver salt (which interacts with the functional silane) and a silver complexing agent. These can be provided as solids or in an aqueous solution.
- The third composition, a reducing composition, comprises a reducing agent for the silver salt, which can be provided as a solid or in an aqueous solution.
- The aqueous graphite activation composition comprises graphite powder and a nitrogen-containing silane. The silane is either a siloxane or a silanol.
- Graphite powder has a minor amount (in the ppm range) of oxygen associated on its surface; the oxygen is capable of interacting in aqueous conditions with the silane in the nitrogen-containing silane to form silanol groups by hydrolysis. This reaction anchors the nitrogen-containing silane to the graphite.
- The nitrogen in the nitrogen-containing silane in turn will coordinate with the silver salt in the silver-plating composition. This coordination provides an activation or seeding site for plating silver on the whole graphite surface.
- Exemplary nitrogen-containing silanes include 3-isocyanatopropyltri-ethoxysilane, 3-isocyanatopropyltrimethoxysilane, 2-cyanoethyltrimethoxy-silane; 2-cyanoethyltriethoxysilane, 3-cyanopropyltri-methoxysilane, 3-cyano-propyltriethoxysilane, 3-cyanopropylmethyldimethoxysilane, 3-aminopropyl-trimethoxy-silane, 3-aminopropyltriethoxysilane, 3-amino-propylmethyl-dimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-amino-butyltriethoxy-silane, N-(2-amino-ethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxy-silane, N-(2-aminoethyl)-3 -aminopropylmethyldimethoxy-silane, aminopropyl-silanetriol, N-(2-aminoethyl)-3-amino-propylsilanetriol, aminophenyltrimethoxy-silane, 3-thiocyanato-propyltriethoxy-silane, and 3-(2-imidazolin-1-yl)propyltriethoxy-silane). Any of these can be used in combination with the others.
- In one embodiment, the nitrogen-containing silane is present in the graphite activation composition in an amount of 0.01-20 weight% of graphite weight, preferably at 0.1-10 wt% of graphite weight.
- The silver-plating composition comprises a silver salt and a silver complexing agent. In one embodiment, the silver salt is water soluble. Exemplary silver salts include silver nitrate, silver sulfate, and silver chloride. In one embodiment, the silver salt is silver nitrate.
- The concentration of silver salt in the plating bath ranges from 0.01 to 50 g/L. In one embodiment, the silver salt concentration ranges from 2 to 30 g/L. In a further embodiment, the silver salt concentration ranges from 5 to 25 g/L.
- Exemplary silver complexing agents include ammonium hydroxide, ethylenediamine, methylamine, and ethylamine. In one embodiment, the complexing agent is ammonium hydroxide in an aqueous solution within the range of 28 to 30 wt% (weight percent). The amount of 28 to 30 wt% ammonium hydroxide solution present in the plating bath ranges from 0.01 to 35 g/L; in one embodiment, from 1.4 to 20 g/L; in a further embodiment, from 3.5 to 18 g/L.
- The silver-plating composition can be mixed in conjunction with the graphite activation composition or added separately, after the graphite composition is formed and mixed.
- The reducing composition comprises a reducing agent for the silver salt. Exemplary reducing agents include aldehydes, polyols, tartrates, tartaric acid, monosaccharides, disaccharides, polysaccharides, hydrazine, hydrazine hydrate, and phenyl hydrazine.
- In one embodiment, the reducing agent is formaldehyde (typically as a 37 wt% aqueous solution) and/or glyoxal (typically as a 40 wt% aqueous solution). In the embodiment in which the reducing agent is formaldehyde, the amount of 37wt% aqueous formaldehyde solution present in the plating composition ranges from about 0.01 to 150g/L; in another embodiment, from 1 to 100 g/L; in a further embodiment, from 5 to 50 g/L.
- The reducing composition is added to the combination of the graphite activation composition and the silver-plating composition.
- The use of a pH-control substance is optional. Exemplary pH control agents include KOH, NaOH, or any ammonium, nitrate, or borate salt.
- The use of an organic co-solvent is optional. Exemplary co-solvents include alcohol, acetone, tetrahydrofuran (THF), ethyl acetate, and toluene.
- The process of this invention comprises (A) mixing together in water the following compositions: (1) a graphite activation composition comprising graphite powder and a nitrogen-containing silane; (2) a silver-plating composition comprising a silver salt and a silver complexing agent; and (3) a reducing composition for the silver salt; and (B) isolating the resultant silver-coated graphite.
- The components within each of the graphite activation and silver-plating compositions can be mixed together all at once, or they can be mixed in stages with a time delay between additions of the components for mixing to occur. (The reducing composition has only one component.) Mixing is typically accomplished by stirring at room temperature.
- In one embodiment a portion of the silver salt that would make up the silver-plating composition is added to the graphite activation composition. This portion of the silver salt will be an amount within the range of 0.1 wt% to 10 wt% of the total graphite weight. In one embodiment, the silver salt is added to the graphite activation composition in an amount within the range of 1 wt% to 5 wt% of the total graphite weight. The silver-plating composition, less the amount of silver salt previously added to the graphite activation composition, is then added to the graphite activation composition and mixed. To this mixture is added the reducing composition for the silver salt.
- The mixture of compositions is stirred together at a temperature sufficient to cause the silver salt to be reduced and plated onto the graphite. In the plating process containing formaldehyde solution, the preferred mixing temperature or range of mixing temperatures is within the range of 20°C to 25°C. The typical reaction time is under one hour for laboratory quantities; however, longer times can be expected for commercial quantities.
- Glyoxal is a possible substitute for formaldehyde; however, it is less reactive and requires a higher reaction temperature and longer mixing. A benefit is that it has less toxicity.
- The graphite activation, silver-plating, and reducing compositions can be mixed together without any time delay between addition of the compositions to each other. In other embodiments the addition takes place sequentially so that the graphite activation composition is prepared first and mixed for a time; then the silver-plating composition (prepared and mixed) is added to the graphite activation composition. The graphite activation and silver-plating compositions are mixed for a time, after which the reducing composition (prepared and mixed) is added to the combination of the graphite activation and silver-plating compositions, and all three compositions are mixed. Mixing is typically accomplished by stirring at room temperature.
- Example 1. The graphite activation composition and the silver-plating composition were prepared as one composition together, after which the reducing composition was added. The compositions were prepared and mixed at room temperature.
- In a two liter beaker were added 3-isocyanatopropyltriethoxysilane (0.1g), graphite (3 g), and an aqueous solution of silver ammonium nitrate containing silver nitrate (11 g), ammonium hydroxide (28 wt%, 9 g), and water (1000 mL). The mixture was stirred for 45 minutes at room temperature. To this was added with stirring a mixture of reducing agent containing formaldehyde (37 wt%) aqueous solution (10 g). Silver-coated graphite product was formed within 15 minutes and settled to the bottom of the reaction flask. The clear aqueous layer was decanted off and the silver-coated graphite product washed three times with 200g of water each time, followed by drying at 120°C overnight. The yield was above 95%.
- Example 2. The graphite activation composition, containing a small amount of silver nitrate as a seeding compound, was prepared independently of the silver-plating composition. The compositions were prepared and mixed at room temperature.
- In a two liter beaker were added 3-isocyanatopropyltriethoxysilane (0.1g), silver nitrate (0.1g), water (200mL), graphite (3 g). The mixture was stirred for 30 minutes at room temperature. An aqueous silver plating solution containing silver nitrate (11 g) and ammonium hydroxide (28 wt%, 9 g) and water (800mL) was added to the graphite mixture. The combined solutions were stirred for 15 minutes. To this was added with continued stirring a mixture of reducing agent containing formaldehyde (37 wt%) aqueous solution (10 g). Silver-coated graphite product was formed within 15 minutes and settled to the bottom of the reaction flask. The clear aqueous layer was decanted off and the silver-coated graphite product was washed three times with 200g of water each time, followed by drying at 120°C overnight. The yield was above 95%.
- Example 3. A seed solution of silver nitrate was added to a prepared and stirred graphite activation composition. Subsequently, the silver-plating composition was added. The compositions were prepared and mixed at room temperature.
- In a two liter beaker were added 3-isocyanatopropyltriethoxysilane (0.1g), water (200mL) and graphite (3.0g). This mixture was stirred for 15 minutes at room temperature. An aqueous solution of silver nitrate (0.1g) in water (10 mL) was added to the graphite mixture. Stirring was continued for 15 minutes, after which an aqueous silver plating solution containing silver nitrate (11 g), ammonium hydroxide (28 weight%, 9 g) and water (800mL) was added with stirring to the graphite mixture for another 15 minutes at room temperature. To this was added with continued stirring a mixture of reducing agent containing formaldehyde (37 wt%) aqueous solution (10g). Silver-coated graphite product was formed within 15 minutes and settled to the bottom of the reaction flask. The clear aqueous layer was decanted off and the silver-coated graphite product washed three times with 200g of water each time, followed by drying at 120°C overnight. The yield was above 95%.
- Example 4. Comparative. In this example, a prior art multi-step electroless plating method is described as a conventional way of preparing silver-coated graphite material. The method includes the use of graphite activation, graphite sensitization, and plating baths. Moving from bath to bath requires separation of solution and powder product in order to minimize cross contamination of the baths.
- In a 250 mL flask was added a graphite activation solution containing SnCl2·2H2O (0.5g), HCl (37 wt% solution) (0.3g), water (100mL) and graphite (3g). This activation mixture was stirred for 30 minutes at room temperature; centrifuged to settle the graphite and the solution decanted off. The activated graphite mixture was washed once with 60g water, and then added to a graphite sensitization bath containing PdCl2 (0.05g), HCl (37 wt % solution) (0.1g) and water (100mL). The sensitizing mixture was stirred for 30 minutes, centrifuged to settle the graphite, and the sensitization solution removed.
- The sensitized graphite mixture was then washed with 200g water followed by centrifugation until the solution pH reached between 5-6. An aqueous silver plating solution containing silver nitrate (11 g), ammonium hydroxide (28 wt%, 9 g) and water (1100mL) was added with stirring to the sensitized graphite mixture. To this was added with continued stirring a mixture of reducing agent containing formaldehyde (37 wt%) aqueous solution (10 g). Silver-coated graphite product formed within 15 minutes and settled to the bottom of the reaction flask. The clear aqueous layer was decanted off and the silver-coated graphite product washed three times with 200g of water each time, followed by drying at 120°C overnight. The yield was above 95%.
- Conductive adhesive formulations were prepared from each of the silver-coated graphite products from examples 1 to 4 using an epoxy resin (EPICLON 835 LV from DIC formally known as Dainippon Ink and Chemical) at a 32 volume% (vol%) loading of the silver-coated graphite, and one weight% (wt%) of 2-ethyl-4-methyl imidazole based on total weight.
- Films of the formulations were cast on glass slides and cured at 175°C for one hour in an air oven. The film dimensions were: length=75 mm, width=5mm, thickness=0.1mm.
- Volume resistivity (VR) was tested using a four-probe testing method at room temperature. The resistivities were the following:
Example 1 2 3 4 Method One-pot One-pot One-pot Multiple baths VR in 32 vol% (epoxy) (ohm·cm) 1.36E-03 1.34E-03 1.52E-03 3.21E-03 - The results indicate that the one-pot electroless plating processes from examples 1-3 produce silver-coated graphite materials giving higher conductivity than those prepared from the conventional multiple-step process of example 4.
- Example 6. Conductivity Performance in Acrylate Formulations. Conductive adhesive formulations were prepared from each of the silver-coated graphite products from examples 1 to 4 using an acrylate formulation at a 26 vol% loading of the silver-coated graphite (or about 60wt% filler loading based on total weight).
- The acrylate composition contained 49 wt% tricyclodecane dimethanol diacrylate, 46 wt% isobornyl methacrylate, and 5 wt% dicumin peroxide.
- Films of the formulations were cast on glass slides and cured at 175°C for one hour in an N2 oven. The film dimensions were: length=75 mm, width=5mm, thickness=0.1mm.
- Volume resistivity (VR) was tested using a four-probe testing method at room temperature. The resistivities were the following:
Example 1 2 3 4 Method One-pot One-pot One-pot Multiple baths VR in 26vol% (acrylate) (ohm·cm) 4.2 E-03 1.6 E-03 1.5 E-03 1.4 E-02 - The results indicate that the one-pot electroless plating processes from examples 1-3 produce silver-coated graphite materials giving higher conductivity than those prepared from the conventional multiple-step process of example 4.
- Silver-coated graphite samples (SCG) were prepared according to example 2 at various silver-loadings based on total SCG weight. For each selected silver-loading, a comparative SCG sample was also prepared without using a silane activator in the process.
- Adhesive formulations were prepared using the silver-coated graphite (SCG) and its comparative sample. Adhesive resin was either an epoxy composition or an acrylate composition.
- The epoxy compositions contained epoxy resin (EPICLON 835 LV from DIC formally known as Dainippon Ink and Chemical) with 2.5 wt% 2-ethyl-4-methyl-imidazole.
- The acrylate compositions contained 49% tricyclodecane dimethanol diacrylate, 46 wt % isobornyl methacrylate, and 5 wt % dicumin peroxide.
- The silane activator was 3-isocyanatopropyltri-ethoxylsilane (ICPTES).
- Films of the formulations were cast on glass slides. The film dimensions were: length=75 mm, width=5mm, thickness=0.1mm.
- The epoxy formulations were cured at 175°C for one hour in an air oven.
- The acrylate formulations were cured at 175°C for one hour in an N2 oven.
- Volume resistivity (VR) was measured using a four-probe testing method at room temperature.
- The results are set out in the following table and show suitable resistivity for commercial applications.
Sample Total % Ag in SCG N-Silane (wt% of graphite) VR for 60wt% SCG in Epoxy (ohm.cm) VR for 60wt% SCG in Acryl (ohm.cm) A 30% 3.3% 9.5E-01 6.7E-02 A (Comparative) 30% 0% 1.5E+00 1.7E-01 B 40% 3.3% 2.0E-01 1.4E-02 B (Comparative) 40% 0% 2.0E+00 2.5E-01 C 70% 3.3% 2.2E-03 9.2E-04 C (Comparative) 70% 0% 1.4E-02 1.2E-02 - The results also indicate that silver-coated graphite materials giving higher conductivity were produced when a nitrogen-containing silane activator (N-Silane) was used, compared to when no nitrogen-containing silane activator was used, in the one-pot electroless plating processes.
- Silver-coated graphite (SCG) samples were prepared according to example 2 with a nitrogen-containing silane activator as listed in the following table.
- Conductive adhesive formulations were prepared from each of the silver-coated graphite samples using an epoxy resin (EPICLON 835 LV from DIC formally known as Dainippon Ink and Chemical) at a 26 vol% loading of the silver-coated graphite, and one wt% of 2-ethyl-4-methyl imidazole based on total weight.
- Films of the formulations were cast on glass slides. The films had dimensions: length=75 mm, width=5mm, thickness=0.1mm.
- The epoxy formulations were cured at 175°C for one hour in an air oven.
- Volume resistivity (VR) was measured using a four-probe testing method at room temperature.
- The results are set out in the following table and show suitable resistivity for commercial applications.
Sample Total % Ag in SCG N-Silane activator N-Silane (wt% of graphite) VR for 26vol% SCG in Epoxy (ohm.cm) A 70% None 0% 1.4E-02 B 70% 3-isocyanato-propyltriethoxysilane 3.3% 2.2E-03 C 70% 3-cyano-propyltriethoxysilane 3.3% 5.4E-03 D 70% 3-amino-propyltrimethoxysilane 3.3% 5.5E-03 E 70% N-(2-aminoethyl)-3-aminopropyltrimethoxysilane 3.3% 5.5E-03 F 70% aminopropyl-silanetriol 3.3% 5.5E-03 - The results also indicate that silver-coated graphite materials giving higher conductivity were produced when a nitrogen-containing silane activator was used compared to when no silane activator was used in the one-pot electroless plating process.
- Silver-coated graphite (SCG) samples were prepared according to example 2, and were formulated with different concentrations of silane activator, silver nitrate seed, silver nitrate in plating solution, and reducing agent.
- Conductive adhesive formulations were prepared from each of the silver-coated graphite samples and an epoxy resin (EPICLON 835 LV from DIC formally known as Dainippon Ink and Chemical) at a 26 vol% loading of the silver-coated graphite, and one wt% of 2-ethyl-4-methyl imidazole based on total weight.
- Films of the formulations were cast on glass slides. Films had dimensions: length=75 mm, width=5mm, thickness=0.1mm.
- The epoxy formulations were cured at 175°C for one hour in an air oven.
- Volume resistivity (VR) was measured using a four-probe testing method at room temperature.
- The results are set out in the following table and show suitable resistivity for commercial applications with variables in the formulation. The relatively lower amounts of N-silane activator appeared to give the better conductivity values compared to no activator or a higher amount of activator.
Sample Graphite in Plating Solution (g/L) Total % Ag in SCG N-Silane (wt% of graphite) AgNO3 seed (wt% of graphite) AgNO3 in Plating Solution (g/L) H2CO (37%) in plating solution (g/L) VR for 26 vol% SCG in Epoxy ohm.cm A 2.7 70% 0% 3.3% 10 9 (1.9 X AgNO3 mole) 1.4E-02 B 2.7 70% 0.1% 3.3% 10 9 (1.9 X AgNO3 moles) 5.6E-03 C 2.7 70% 10% 3.3% 10 9 (1.9 X AgNO3 moles) 2.2E-03 D 0.55 70% 3.3% 1.5% 2 6 (6.3 X AgNO3 moles) 3.9E-03 E 2.73 70% 0.3% 0.3% 20 18 (1.9 X AgNO3 moles) 9.6E-03
Claims (14)
- A process for the one-pot electroless plating of silver on graphite comprising(A) mixing together in water the following compositions:(1) a graphite activation composition comprising non-pretreated graphite powder and a nitrogen-containing silane;(2) a silver-plating composition comprising a silver salt and a silver complexing agent; and(3) a reducing composition comprising a reducing agent for the silver salt; and(B) isolating the resultant silver-coated graphite.
- The process according to claim 1 in which the nitrogen-containing silane of the graphite activation composition is selected from the group consisting of 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 2-cyano-ethyltrimethoxysilane; 2-cyanoethyl-triethoxysilane, 3-cyanopropyl-trimethoxy-silane, 3-cyanopropyltriethoxysilane, 3-cyanopropylmethyldi-methoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyl-methyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyl-triethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-amino-ethyl)-3 -aminopropyltriethoxy-silane, N-(2-aminoethyl)-3-aminopropyl-methyl-dimethoxysilane, aminopropylsilanetriol, N-(2-aminoethyl)-3-aminopropyl-silanetriol, aminophenyltrimethoxysilane, 3-thiocyanatopropyl-triethoxysilane, 3-(2-imidazolin-1-yl)propyltriethoxysilane, and any combination of the above.
- The process according to claim 1 in which the nitrogen-containing silane is present in an amount from 0.1 to 10 wt% of the graphite weight.
- The process according to claim 1 in which the silver salt of the silver-plating composition is selected from the group consisting of silver nitrate, silver sulfate, and silver chloride; and in which the silver complexing agent of the silver-plating composition is selected from the group consisting of ammonium hydroxide, ethylenediamine, methylamine, and ethylamine.
- The process according to claim 1 in which the silver salt is present in an amount of 0.01 to 50 g/L of the plating solution.
- The process according to claim 1 in which the reducing agent for the silver salt is selected from the group consisting of aldehydes, polyols, tartrates, tartaric acid, monosaccharides, disaccharides, polysaccharides, hydrazine, and hydrazine hydrate.
- The process according to claim 1 in which the reducing agent for the silver salt is present in an amount of 1 to 50 times the moles of silver salt in the plating solution.
- The process according to claim 1 in which the graphite activation composition further comprises silver salt in an amount of 0.1%-10% of the total graphite weight in the silver-plating composition.
- The process according to claim 5 in which the silver salt, 0.1%-10% of the total graphite, is added to the graphite activation composition before the graphite activation composition and the silver-plating composition are mixed.
- An aqueous electroless plating composition for plating graphite powder with silver comprising:(A) non-pretreated graphite powder present in the range of 0.1-100 g/L;(B) a silver salt, present in the range of 0.01-50 g/L;(C) a silver complexing agent, present in the range of 0.01-35 g/L;(D) a nitrogen-containing silane present in the range of 0.01-20 w% of the graphite weight;(E) a reducing agent for the silver salt, present in the range of 1-50 times the moles of silver salt.
- The plating composition of claim 10 in which the silver salt is selected from the group consisting of silver nitrate, silver sulfate, and silver chloride.
- The plating composition of claim 10 in which the silver complexing agent is selected from the group consisting of ammonium hydroxide, ethylenediamine, methylamine, and ethylamine.
- The plating composition of claim 10 wherein the nitrogen-containing silane is selected from the group consisting of 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 2-cyanoethyltrimethoxysilane; 2-cyanoethyl-triethoxysilane, 3-cyanopropyltrimethoxysilane, 3-cyanopropyltriethoxysilane, 3-cyanopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino-propyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltriethoxysilane, N-(2-aminoethyl)-3 -amino-propyltrimethoxy-silane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyl-methyldimethoxysilane, aminopropylsilanetriol, N-(2-aminoethyl)-3-aminopropylsilanetriol, aminophenyltrimethoxysilane, 3-thiocyanatopropyltriethoxysilane, and 3-(2-imidazolin-1-yl)propyltriethoxysilane.
- The plating composition of claim 10 wherein the reducing agent is selected from the group consisting of aldehydes, polyols, tartrate, tartaric acid, monosaccharides, disaccharides, polysaccharides, hydrazine, and hydrazine hydrate.
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PCT/US2012/028251 WO2013089815A1 (en) | 2011-12-15 | 2012-03-08 | Electroless plating of silver onto graphite |
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CN103998651B (en) * | 2011-12-15 | 2016-11-23 | 汉高知识产权控股有限责任公司 | Chemical silvering on graphite |
KR102208197B1 (en) * | 2019-05-27 | 2021-01-27 | 주식회사 엠엠에스 | Method for producing multi-functional multi-layered powder composed of silver-copper-graphite and Multi-functional multi-layered powder by the method |
KR102231389B1 (en) | 2019-06-12 | 2021-03-24 | 주식회사 엠엠에스코퍼레이션 | Method for manufacturing Electromagnetic wave shielding and heat radiation coating composition containing low specific gravity conductive powder |
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US7282260B2 (en) * | 1998-09-11 | 2007-10-16 | Unitech, Llc | Electrically conductive and electromagnetic radiation absorptive coating compositions and the like |
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TW554348B (en) * | 1999-05-13 | 2003-09-21 | Shinetsu Chemical Co | Conductive powder and making process |
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CN1261618C (en) * | 2000-04-25 | 2006-06-28 | 株式会社日矿材料 | Pretreating agent for plating and method for metal plating using the same |
US6387542B1 (en) * | 2000-07-06 | 2002-05-14 | Honeywell International Inc. | Electroless silver plating |
WO2004108986A1 (en) * | 2003-06-09 | 2004-12-16 | Nikko Materials Co., Ltd. | Method for electroless plating and metal-plated article |
CN1624175A (en) * | 2003-12-02 | 2005-06-08 | 上海电器科学研究所(集团)有限公司 | Electric contact material of carbon nano pipe silver graphite and its preparation process |
US7713340B2 (en) | 2004-01-29 | 2010-05-11 | Nippon Mining & Metals Co., Ltd. | Pretreating agent for electroless plating, method of electroless plating using the same and product of electroless plating |
JP4274090B2 (en) * | 2004-09-17 | 2009-06-03 | ソニー株式会社 | Graphite powder and non-aqueous electrolyte secondary battery |
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CN1919933A (en) * | 2006-09-01 | 2007-02-28 | 清华大学 | Method of preparing electric conductive adhesive by chemical plating silver on graphite powder surface |
JP2008133535A (en) * | 2006-10-26 | 2008-06-12 | Ube Nitto Kasei Co Ltd | Method for producing metal nanoparticle-adhered base material, composition for forming base material adherable metal nanoparticle, method for producing metal layer-coated base material, method for pretreatment to electroless plating, composition for pretreatment to electroless plating, and electroless plated article |
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